Method and apparatus for efficient injection of CO2 in oceans

ABSTRACT

A liquid CO 2  injection system produces a negatively buoyant consolidated stream of liquid CO 2 , CO 2  hydrate, and water that sinks upon release at ocean depths in the range of 700-1500 m. In this approach, seawater at a predetermined ocean depth is mixed with the liquid CO 2  stream before release into the ocean. Because mixing is conducted at depths where pressures and temperatures are suitable for CO 2  hydrate formation, the consolidated stream issuing from the injector is negatively buoyant, and comprises mixed CO 2 -hydrate/CO 2 -liquid/water phases. The “sinking” characteristic of the produced stream will prolong the metastability of CO 2  ocean sequestration by reducing the CO 2  dissolution rate into water. Furthermore, the deeper the CO 2  hydrate stream sinks after injection, the more stable it becomes internally, the deeper it is dissolved, and the more dispersed is the resulting CO 2  plume. These factors increase efficiency, increase the residence time of CO2 in the ocean, and decrease the cost of CO 2  sequestration while reducing deleterious impacts of free CO 2  gas in ocean water.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0001] The United States Government has rights in this invention pursuant to Contract No. DE-AC05-00OR22725 between the United States Department of Energy and UT-Battelle, LLC.

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] The invention relates to methods for direct injection of CO₂ into the ocean for carbon sequestration. More particularly, it relates to the production of a negatively buoyant CO₂ hydrate in the form of a consolidated CO₂-hydrate/CO₂-liquid/water stream that sinks upon release at intermediate ocean depths of about 1000 m.

[0004] 2. Background Information

[0005] The concentration of carbon dioxide (CO₂) in the atmosphere is steadily increasing as a result of both land use changes and the combustion of fossil fuels for energy production. Due to the enhanced greenhouse effect caused by increasing concentrations of CO₂ and other greenhouse gases in the atmosphere (e.g., methane), it is predicted that greater amounts of heat will be retained within the atmosphere leading to a gradual increase in the surface temperature of the earth. Reducing the potential risks of human-induced global climate change will require that means be found to slow the rate of increase in atmospheric CO₂ levels. One of the strategies is to capture and sequester CO₂ by enhancing the natural capacity of the terrestrial biosphere and the oceans to take up and store carbon.

[0006] Direct injection of CO₂ into the ocean has been proposed as a means for carbon sequestration because it offers a large storage capacity for carbon (Herzog 1998). Depending on the depth of injection as well as the subsequent interaction of CO₂ with seawater, the residence time of CO₂ in the ocean can be on the order of several hundred years, leading to significantly reduced rates of atmospheric CO₂ increase as well as lower peak levels. The thermodynamic properties of CO₂ and seawater, in combination with ambient pressure and emplacement methodology, will strongly influence the form and subsequent fate of CO₂ that is injected into the ocean. For example, at depths less than ˜500 m, CO₂ will be a gas and will therefore be more likely to partition back into the atmosphere within decades to centuries. At depths between ˜500 and ˜2600 m, the density of liquid CO₂ is lower than that of seawater. At greater depths, liquid CO₂ is denser than the surrounding seawater. Thus, CO₂ injected at depths between 500 and 2600 m will be in liquid form and will tend to rise (i.e., be positively buoyant), while CO₂ released at depths >2600 m will sink (i.e., be negatively buoyant).

[0007] Direct ocean CO₂ injection will be considered successful if the following conditions are met: the residence time of CO₂ released in the ocean is on the order of several centuries or more; negligible environmental impacts are associated with the release; the energy requirement for the ocean emplacement is small relative to that obtained from CO₂ generation; and the process is cost-effective.

[0008] Several methods for direct CO₂ injection have been suggested. These include: (1) injection at moderate depths of 1000-2000 m through a fixed or towed pipe resulting in a rising liquid CO₂ droplet plume; (2) injections into ocean floor depressions at depths >2600 m forming a CO₂ lake; (3) disposal as dry ice; and (4) shallow discharge as a dense solution of seawater with dissolved CO₂ forming a dense sinking liquid plume. These and other methods are reviewed in the recent papers of Caulfield (1997) and Herzog (1998).

[0009] Because emplacement costs increase significantly with injection depth, the lowest cost is anticipated for the dense-plume approach (alternative 4), which requires injection depths between 500 and 1000 m. However, the low cost of implementation for this approach may be offset by the negative environmental impact on the marine ecosystem that would result from a highly concentrated CO₂ composition and low pH in the vicinity of the sinking dense plume. Injection at depths >1000 m is therefore believed to have lesser environmental impacts and lower rates of release to the atmosphere. A high cost is associated with the CO₂-lake disposal (alternative 2) because of the need for special pipelines that can withstand hydrostatic pressures at the required injection depth (>2600 m) where CO₂ becomes denser than seawater. Dry ice (alternative 3) can be discharged at shallow depths, however, its production and handling cost can be very high.

[0010] When compared to the other disposal alternatives, droplet plume disposal at injection depths of 1000-2000 m (Alternative 1) appears to be the most favorable when factors such as development cost, difficulty and environmental impacts are considered. As CO₂ is only slightly miscible with seawater, the CO₂-seawater system is hydrodynamically unstable, and liquid CO₂ discharged into seawater will break up into droplets due to interfacial instability. The droplets will rise because injection depths are shallower than the ˜2600-m required for CO₂ to be negatively buoyant in seawater. To ensure that the rising CO₂ droplets completely dissolve into the seawater before it reaches depths where CO₂ becomes gaseous (˜500 m), sufficient injection depth (>1500 m) is required.

[0011] The preceding review of current research shows that the positive buoyancy of CO₂ droplets has a negative impact on the long-term environmental success of liquid CO₂ injections at intermediate depths. In addition, although CO₂ is in liquid state at depths >500 m, injections must be performed at depths greater than 1500 m to ensure that rising CO₂ drops dissolve completely before reaching the critical 500-m depth threshold.

[0012] Our invention is a CO₂ injection method based on the production of a new CO₂ injection form, comprising of a consolidated CO₂-liquid/CO₂-hydrate/water paste-like stream, that sinks at shallower depths than other CO₂ forms. To date, no studies discussing generation of a negatively buoyant CO₂-liquid/CO₂-hydrate/water consolidated stream for ocean sequestration have been reported. The result is the achievement of cost savings without the negative environmental impact of other shallow depth injection methods.

REFERENCES

[0013] 1. J. A. Caulfield, D. I. Auerbach, E. E. Adams and H. J. Herzog, “Near Field Impacts of reduced pH from Ocean CO₂ Disposal”, Energy Convers. Mgmt. Vol. 38, pp. S343-348 (1997).

[0014] 2. H. J. Herzog, “Ocean Sequestration of CO₂—An Overview”, Fourth International Conference on Greenhouse Gas Control Technologies, Interlaken, Switzerland, pp. 1-7, Aug. 30-Sep. 2, 1998.

[0015] 3. J. J. Morgan, V. R. Blackwell, D. E. Johnson, D. F. Spencer and W. J. North, “Hydrate Formation from Gaseous CO₂ and Water”, Environ. Sci. Technol. Vol. 33, pp. 1448-1452 (1999).

[0016] 4. S. Hirai, Y. Tabe, G. Tanaka and K. Okazaki, “Advanced CO₂ Ocean Dissolution Technology for Longer Term Sequestration with Minimum Biological Impacts”, Greenhouse Gas Control Technologies, P. Riemer, B. Eliasson and A. Wokaun, editors, Elsevier Science, Ltd., pp. 317-322 (1999).

[0017] 5. A. Yamasaki, M. Wakatsuki, H. Teng, Y. Yanagisawa and K. Yamada, “A New Ocean Disposal Scenario for Anthropogenic CO₂: CO₂ Hydrate Formation in a Submerged Crystallizer and its Disposal”, Energy Vol. 25, pp. 86-96 (2000).

[0018] 6. T. J. Phelps, D. J. Peters, S. L. Marshall, O. R. West, L. Liang, J. G. Blencoe, V. Alexiades, G. K. Jacobs, M. T. Naney and J. L. Heck, Jr., “A New Experimental Facility for Investigating the formation and Properties of Gas Hydrates under Simulated Seafloor Conditions”, Rev. Sci. Instrum. Vol. 72, No. 2, pp. 1514-1521 (2001).

OBJECTS OF THE INVENTION

[0019] It is a first object of the invention to provide a consolidated CO₂-hydrate/CO₂-liquid/water stream that sinks upon release at intermediate ocean depths of about 1000 m.

[0020] Another object of the invention is to reduce pressurization of CO₂ liquid for ocean injection by providing a negatively buoyant CO₂ stream for injection at shallower depths.

[0021] Another object of the invention is to provide a CO₂ injection form having a longer residence time in the ocean.

[0022] A further object of the invention is to dissolve CO₂ slowly, imposing minimal environmental impact.

[0023] A still further object of the invention is to provide efficient and economical CO₂ disposal in the ocean.

[0024] Yet another object of the invention is to provide a CO₂ disposal method that is compatible with current pipeline delivery systems.

BRIEF SUMMARY OF THE INVENTION

[0025] In a first embodiment, the invention is a method for continuous production of a hydrate-containing stream that comprises the steps of delivering a fluid containing hydrate-forming species to a pressurized, temperature controlled, continuous-flow reactor; and mixing the fluid containing hydrate-forming species with water until a consolidated hydrate-fluid-water stream is formed.

[0026] In another embodiment, the invention is a method for sequestering CO₂ in the ocean that comprises the steps of pumping liquid CO₂ into a discharge pipe located at a predetermined ocean depth; pumping seawater from the predetermined ocean depth into the discharge pipe; sufficiently mixing the liquid CO₂ with the seawater from the predetermined ocean depth for a sufficient amount of time until a paste-like consolidated CO₂-hydrate/CO₂-liquid/water stream is formed; and discharging the paste-like consolidated CO₂-hydrate/CO₂-liquid/water stream into the ocean.

BRIEF DESCRIPTION OF THE DRAWINGS

[0027]FIG. 1 illustrates one embodiment of the present invention. Liquid CO₂ is mixed with seawater at a predetermined moderate ocean depth to form a paste-like CO₂-liquid/CO₂-hydrate/water consolidated stream that is discharged into the ocean and sinks because it is heavier than the surrounding seawater at that depth.

[0028]FIG. 2 is a graph of density as a function of pressure and ocean depth for liquid CO₂, seawater, and an example stream of consolidated seawater-CO₂-hydrate phases. The example consolidated stream consists of a 3:1 volumetric ratio of seawater to CO₂ where ˜3% of the CO₂ is in hydrate form. Point A is where the consolidated stream becomes neutrally buoyant in seawater. Point B is where pure CO₂ becomes neutrally buoyant.

[0029]FIG. 3 is a series of photographs showing the production of a consolidated stream of CO₂-liquid/CO₂-hydrate/water achieved by mixing water with liquid CO₂ before injection in water at a temperature of 5° C. and a pressure equivalent to 1300 m of water. FIG. 3(a) shows a drop of liquid CO₂ released in water with no premixing with water; FIG. 3(b) shows the transition from drops to a consolidated stream by mixing liquid CO₂ with water; FIG. 3(c) shows a steady flow of the negatively buoyant consolidated stream; and FIG. 3(d) shows the injector at continuous operation.

[0030]FIG. 4 is a photograph showing the injector of FIG. 3 mounted horizontally in the SPS test facility. The negatively buoyant consolidated stream of CO₂-liquid/CO₂-hydrate/water phases is produced at a pressure equivalent to a 1300-m ocean depth. The stream is observed to bend downward due to its negative buoyancy.

DETAILED DESCRIPTION OF THE INVENTION

[0031] The CO₂ injection system of this invention is designed to produce a paste-like negatively buoyant seawater CO₂-hydrate/CO₂-liquid/water consolidated stream that sinks upon release at shallow ocean depths (−1000 m) as an alternative to other current CO₂ ocean disposal methods. In this approach, seawater is mixed with the liquid CO₂ stream before release into the ocean. Because mixing is conducted at depths where pressures and temperatures are suitable for CO₂ hydrate formation, a negatively buoyant consolidated stream comprising mixed CO₂-hydrate/CO₂-liquid/water phases issues from the injector. The negatively buoyant consolidated stream, in combination with a slower dissolution rate for CO₂ hydrates, prolong the metastability of CO₂ ocean sequestration.

[0032] The invention utilizes intense mixing of liquid CO2 and seawater to form many hydrate-encased seawater and CO2 droplets (primary particles) which then consolidate into a paste-like CO₂-liquid/CO₂-hydrate/water stream. A higher water volume fraction will lead to a CO₂-liquid/CO₂-hydrate/water consolidated stream with a higher bulk density because (1) more CO₂ hydrate will be formed (density=1.12 g/mL) and (2) the stream will contain less CO₂ liquid, which has lower density than water.

[0033] Details of the invention are shown in FIG. 1. A discharge pipe 15 is maintained at a predetermined ocean depth, and liquid CO₂ is pumped into the pipe 15. Seawater from the predetermined ocean depth is pumped into the pipe 15 through a second pipe 16. By this means, the seawater and liquid CO₂ are contacted in the pipe 15 at high Reynolds numbers to ensure turbulent conditions. Intense mixing at the point of contact leads to the formation of fine water droplets in CO₂.

[0034] The formation of droplets increases the interfacial area between the water and CO₂phases, which enhances the rate of CO₂ hydrate formation. By adjusting the residence time of the fluid in the nozzle, the ratio of the three phases (water, CO₂ hydrate, and liquid CO₂) can be controlled at the exit of the nozzle. The composition of the three phases determines the bulk density of the stream. Since CO₂ hydrate has a density higher than water, it is possible to have a consolidated stream of the three phases with higher bulk density than the surrounding water.

[0035] The mixing of seawater with a liquid CO₂ stream using the CO₂ injection device shown in FIG. 1 is thus able to produce a negatively buoyant hydrate-containing stream at shallower depths, potentially reducing the cost and minimizing the risk of CO₂ being released back to the atmosphere. The concept underlying the injection system design is further shown in FIG. 2, in which densities are plotted vs. ocean depth (or pressure) for seawater; liquid CO₂ (at 2° C.); and a paste-like stream consisting of consolidated CO₂-hydrate/CO₂-liquid/water phases. The paste-like stream was formed by mixing seawater and CO₂ at a 3:1 volumetric ratio, and ˜3% of the CO₂ was assumed to be converted to hydrate. Because the density of CO₂ hydrate is ˜10% greater than that of seawater, a consolidated stream containing a small amount of CO₂ hydrate can have a higher bulk density than that of the surrounding seawater at ˜1100 m (FIG. 2, Point A). Thus, this consolidated stream will sink when released at a minimum depth of 1100 m, 1500 m shallower than the depth at which pure CO₂ (at 2° C.) is denser than seawater (FIG. 2, Point B).

[0036] Various mixing devices can be designed to form CO₂hydrate/CO₂-liquid/water consolidated streams. The common features of these devices are: (1) contacting seawater with CO₂ in a wide range of water volume fractions to form an emulsion where small drops of one fluid are dispersed into the other fluid, and (2) allowing a sufficient time for CO₂ hydrate to be formed on the interfacial areas between the CO₂ and seawater in the emulsion, eventually forming a paste-like consolidated stream of CO2 hydrate-liquid CO2-seawater phases. Examples of specific mixing devices include static or electrically-powered mixing blades emplaced in the CO₂ discharge pipeline section where CO₂ and water come together. Entrainment and mixing of seawater with the CO₂ in the CO₂ discharge pipeline can also be achieved through a venturi or jet pump.

[0037] A laboratory test facility known as the Seafloor Process Simulator (SPS, Phelps 2001) located at the Oak Ridge National Laboratory was used to produce the consolidated CO₂ hydrate of this invention using a laboratory-scale version of the injector shown in FIG. 1. The SPS is made from Hastelloy C-22 (selected for resistance to seawater corrosion) with a reaction volume of 70 L (31.75-cm internal diameter, 91.4-cm internal height). A refrigerated, walk-in cooler provides temperature control for the vessel. The vessel is equipped with sapphire windows for visual observations and recording, as well as sampling ports for material collection and measuring devices such as thermocouples, pressure transducers, and pH probes. The vessel is also equipped with fluid delivery and recovery systems that allows fluid flow while maintaining constant pressurization. The SPS provides a well-controlled environment for conducting experimental simulations of liquid CO₂ injection on a small scale.

[0038] As expected from the prior art, injections in which seawater was not premixed with the CO₂ stream produced rising droplets of liquid CO₂, which eventually formed a thin translucent shell of CO₂ hydrate. By introducing water into liquid CO₂ through a capillary tube at varying flow-rate ratios, a paste-like stream of consolidated phases of CO₂ hydrate, liquid CO₂, and water under conditions typical of intermediate ocean depths (i.e., temperature=3-4° C., pressure=10.3-13.1 MPa) was achieved. This result is illustrated in FIG. 3, which shows the injector mounted vertically in the SPS in the direction of negative buoyancy. The photographs correspond to (a) a drop of liquid CO₂ released in water with no premixing with water; (b) transition from drops to a consolidated stream by mixing liquid CO₂ with water; (c, d) steady production of the negatively buoyant consolidated stream at 13.1 MPa, corresponding to 1300-m depth. More evidence for the negative buoyancy of the stream of hydrate-CO₂-water is shown in FIG. 4. In this case, the injector was positioned horizontally in the vessel and the injected stream is observed to bend downward because of its higher bulk density relative to that of seawater. We have also been able to generate a negatively buoyant CO₂ stream at pressures as low as 10.3 MPa, which corresponds to an ocean depth of ˜1000 m.

[0039] Based on several sets of experiments in the SPS using both fresh and artificial seawater (3.5% NaCl), we have found that the density of the hydrate stream produced by our injection system depends on the ratio of water and liquid CO₂ flow rates, the total flow rate through the injector, the pressure at the injection point, and the mixing energy. A sinking stream was consistently produced if the ratio of the water to liquid CO₂ flow rates is greater than 3. However, lower water-to-liquid CO₂ flow rates are possible under better mixing conditions. The required flow-rate ratio appears to increase with decreasing pressure. For example, for 10.3 and 13.1 MPa, the water-to-CO₂ ratios of 5 and 3 are required, respectively. A stream composed of a 25:8 volumetric mixture of liquid CO₂ and water progressed from positive to negative buoyancy as the pressure was increased from 10.3 MPa to 13.1 MPa. The effect of higher pressure likely results from a greater driving force for the conversion of CO₂ to CO₂ hydrate, as well as the presence of compressible liquid Co₂ in the consolidated stream. A greater mixing intensity, which occurs at higher total flow rates through the injector, provided a larger interfacial area between water and liquid CO₂, thus increasing the mass transfer rate between CO₂ and water and increasing the surface areas on which hydrates can nucleate and grow. Therefore, the combination of higher pressure and mixing intensity lead to a greater reaction rate for CO₂ hydrate formation and an increase in the bulk density of the hydrate stream produced by our injector.

[0040] Using our method of premixing seawater into a CO₂ stream, a negatively buoyant CO₂ hydrate-liquid CO₂-water stream is able to be produced at intermediate ocean depths (˜700 to 1500 m). Such a development is significant because it generates a sinking stream at depths <1500 m, and will prolong the metastability of CO₂ in seawater. Because implementation costs increase significantly with injection depth, this approach allows CO₂ injections to be performed not only with a lower risk of leakage to the atmosphere but also without significant increase in operating cost when compared with other proposed injection methods. Also, because of its low surface-to-volume ratio, the produced stream is expected to have a slower dissolution rate than that of a similar volume of liquid CO₂ in the form of a droplet plume. This slower rate will reduce the potential for low-pH conditions surrounding the injector, thereby decreasing the negative impact of direct CO₂ injections on the ocean environment.

[0041] While there has been shown and described what are at present considered the preferred embodiments of the invention, it will be obvious to those skilled in the art that various changes and modifications can be prepared therein without departing from the scope of the inventions defined by the appended claims. 

We claim:
 1. A method for continuous production of a hydrate-containing stream comprising: delivering a fluid containing hydrate-forming species to a pressurized, temperature controlled, continuous-flow reactor; and mixing said fluid containing hydrate-forming species with water until a consolidated hydrate-fluid-water stream is formed.
 2. The method of claim 1 wherein said continuous-flow reactor comprises: a pipe for receiving said fluid containing hydrate-forming species; means for controlling the flow rate of said fluid containing hydrate-forming species into said pipe; means for introducing and controlling the flow rate of said water to said fluid containing hydrate-forming species in said pipe; temperature control means for controlling the temperature of said pipe; and a pressure control device for controlling the pressure within said continuous-flow reactor.
 3. The method of claim 2 wherein said means for controlling the flow rate of said fluid containing hydrate-forming species is a mass flow controller.
 4. The method of claim 2 wherein said means for introducing and controlling the flow rate of said water to said fluid containing hydrate-forming species in said pipe is a pump equipped with a flow controller.
 5. The method of claim 2 wherein said means for introducing and controlling the flow rate of said water to said fluid containing hydrate-forming species in said pipe is a jet pump.
 6. The method of claim 2 wherein said pipe further includes static mixing blades for mixing said fluid containing hydrate-forming species and said water.
 7. The method of claim 2 wherein said pipe further includes electrically powered mixing blades for mixing said fluid containing hydrate-forming species and said water.
 8. A method for sequestering CO₂ in the ocean comprising the steps of: pumping liquid CO₂ into a discharge pipe located at a predetermined ocean depth; pumping seawater from said predetermined ocean depth into said discharge pipe; sufficiently mixing said liquid CO₂ with said seawater from said predetermined ocean depth for a sufficient amount of time until a paste-like consolidated CO₂-hydrate/CO₂-liquid/water stream is formed; and discharging said paste-like consolidated CO₂-hydrate/CO₂-liquid/water stream into the ocean.
 9. The method of claim 8 wherein said ocean depth is greater than 700 m, such that pressures are sufficiently high for CO₂ hydrate to be stable.
 10. The method of claim 8 wherein said CO₂ temperature and said seawater temperature are less than the temperature for CO₂ hydrate stability corresponding to said predetermined ocean depth.
 11. The method of claim 8 wherein the flow rate ratio of said seawater flow to said liquid CO₂ fluid flow is greater than 0.4. 